EP3277407B1 - Process for the absorption of carbon dioxide - Google Patents

Process for the absorption of carbon dioxide Download PDF

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Publication number
EP3277407B1
EP3277407B1 EP16716640.4A EP16716640A EP3277407B1 EP 3277407 B1 EP3277407 B1 EP 3277407B1 EP 16716640 A EP16716640 A EP 16716640A EP 3277407 B1 EP3277407 B1 EP 3277407B1
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EP
European Patent Office
Prior art keywords
carbon dioxide
liquid
gas
process according
fluidised bed
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Active
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EP16716640.4A
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German (de)
French (fr)
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EP3277407A1 (en
Inventor
Howard Paul Davis
David William Missions
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Fluid Technologies Environmental Ltd
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Fluid Technologies Environmental Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
    • B01D47/14—Packed scrubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
    • F23J15/04—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material using washing fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/95—Specific microorganisms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • B01D2252/103—Water
    • B01D2252/1035—Sea water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/56—Use in the form of a bed
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/32—Direct CO2 mitigation

Definitions

  • the present invention provides a method for capturing Carbon Dioxide (CO 2 ) from flue gas & waste gas streams in to liquid at a high efficiency (or at a required efficiency) without the need for liquid or aqueous reagents such as Amines and Carbonates.
  • CO 2 Carbon Dioxide
  • This is another costly step, which is facilitated by changes in pressure, temperature or chemical equilibrium or by applying a second reagent to 'unlock' the CO 2 and release it in a more usable state.
  • WO2011/014957A1 and WO011/014955A1 describe absorption concepts for CO 2 in packed bed reactors.
  • CO 2 recovered in carbon capture plants can be used for Enhanced Oil Recovery or for Growth Enhancement of horticultural crops, fruits & flowers in glasshouses.
  • the result is a surprisingly efficient method for capturing carbon and quickly releasing it (from a fluidised bed or other desorber or stripper), which overcomes the need for expensive consumable reagents or application of heat, pressure and additives for CO 2 release and reagent regeneration purposes.
  • salt or saline solutions can include any dissolvable salt up to, and even beyond, its solubility limit such that the solution is maintained at saturation.
  • the important thing is to use an existing saline solution such as brackish or sea water or to increase the salt concentration of a town or process water such that the Ionic Strength of the solution has at least a value of 0.2 mol/litre.
  • Soluble salts that can be used to boost the Ionic Strength of the resultant saline solution include Chlorides, Bromides, Iodides, Chlorates, Sulphates, Sulphides,
  • the present invention provides an improved process for carbon capture in accordance with the claims appended hereto.
  • the CO 2 was captured in to a semi saturated aqueous solution of Calcium Chloride of about 50% of its pure CaCl 2(aq) solubility limit in water at 12°C, (i.e. at about 31.5g of CaCl 2(c) per 100g of water or 2.84mol/litre) being the average temperature of the tested saline solution through the scrubber tower, the saline solution having an Ionic Strength of about 8.5mol/litre.
  • FIG. 2 One proposed application of the process is shown in Figure 2 , whereby the CO 2 is captured from a dirty flue gas in a fluid bed scrubber (TurboScrubber RTM ) then cycled rapidly to a fluid bed stripper (TurboStripper RTM ) where it is desorbed in to a clean air stream for introduction to a horticultural glass-house to enhance fruit, vegetable or other crop growth.
  • a fluid bed scrubber TroboScrubber RTM
  • TurboStripper RTM fluid bed stripper
  • FIG. 3 Another proposed application of the novel process provided by the present invention is illustrated in Figure 3 , in which process, either CO 2 enriched salt water is circulated through a tank 7 containing Algae to feed the Algae, to allow fast photosynthesis to occur in, for example, the production of bio-fuels, or the Algae suspension, if sufficiently robust, can be pumped around the Turboscrubber RTM 2 and the Algae tank 7 to keep it in constant contact with the CO 2 enriched aqueous solution.
  • the Turboscrubber RTM is provided with:
  • the Algae tank 7 comprises an optional stirrer 9, a bleed valve 8 and on outlet line with a return pump 10 in a line 10a for recirculating treated flue gas to the Turboscrubber RTM 2.
  • Algae recycling line 4 is provided between the line 5 and the recirculating line 10a, see Figure 3 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)

Description

  • The present invention provides a method for capturing Carbon Dioxide (CO2) from flue gas & waste gas streams in to liquid at a high efficiency (or at a required efficiency) without the need for liquid or aqueous reagents such as Amines and Carbonates.
  • Currently in order to fulfil the requirement for higher efficiency carbon capture, thus enabling useful transfer to products or storage in a more manageable form, chemical reactions which enhance liquid absorption of CO2 by reacting with it within the liquid interface are widely employed.
  • Once captured the CO2 may have to be released into a more concentrated stream such that it becomes necessary to reverse the chemical reaction which binds it (e.g. K2CO3(aq) + CO2(aq) + H2O(1) = 2KHCO3(aq)). This is another costly step, which is facilitated by changes in pressure, temperature or chemical equilibrium or by applying a second reagent to 'unlock' the CO2 and release it in a more usable state.
  • WO2011/014957A1 and WO011/014955A1 describe absorption concepts for CO2 in packed bed reactors.
  • Typically CO2 recovered in carbon capture plants can be used for Enhanced Oil Recovery or for Growth Enhancement of horticultural crops, fruits & flowers in glasshouses.
  • By combining the unique properties of counter-current fluidised bed gas scrubbers, which employ fluidisable elements, being hollow or low density solid elements, usually manufactured in plastic materials, with the use of non-reacting salt or saline solutions, a more advantageous result is achieved.
  • The result is a surprisingly efficient method for capturing carbon and quickly releasing it (from a fluidised bed or other desorber or stripper), which overcomes the need for expensive consumable reagents or application of heat, pressure and additives for CO2 release and reagent regeneration purposes.
  • The unique properties of fluid bed gas scrubbers that allow the combinatory effects to function are;
    1. a) Impossible to cause 'Flooding';
    2. b) The use of high liquid to gas (L/G) ratios without excessive gas pressure loss;
    3. c) Generation of high interfacial areas particularly with eccentric shapes; and,
    4. d) Salting out (precipitation of salts above the solubility limit) will not block the fluidised bed, which can handle high percentage slurries, or hinder the process
  • By applying these advantages in combination with the use of salt solutions in water it becomes possible to raise capture efficiencies (CO2 removal percentage) to well above 50%, which is otherwise not achievable except by employing costly and inherently complicated reacting systems.
  • Typically salt or saline solutions can include any dissolvable salt up to, and even beyond, its solubility limit such that the solution is maintained at saturation. The important thing is to use an existing saline solution such as brackish or sea water or to increase the salt concentration of a town or process water such that the Ionic Strength of the solution has at least a value of 0.2 mol/litre.
  • In addition to the requirement for elevated salt concentration, other simultaneous conditions needed to create the required high removal efficiencies (typically greater than 10% absorption is needed for most applications using CO2) are to have CO2(g) partial pressures in gas above 1% v/v and L/G ratios, litres/m3, in excess of 20.
  • At L/G ratios at this level packed towers and sieve plate or tray columns would flood and spray towers would give insufficient interphase surface between the ascending gas and the descending liquid within the scrubber body.
  • Soluble salts that can be used to boost the Ionic Strength of the resultant saline solution include Chlorides, Bromides, Iodides, Chlorates, Sulphates, Sulphides,
  • Sulfites, Bicarbonates & Phosphates and even Hydroxides & Carbonates which react with CO2(aq). However, when using rapid desorption (stripping), as in the arrangement
  • Figure 2, following absorption the CO2(aq), reactions with these latter two compound groups will be too slow to take effect before the Carbon Dioxide is removed, as required, from the process such that the physical properties of the salts, in helping to effect fast capture of the CO2(g), are not intererfered with by the reactive properties, which would otherwise convert the useful CO2 to Bicarbonates and Carbonates A few examples of appropriate salts are CaCl2, NaCl, KCl, K2CO3, KHCO3, Na2CO3, NaHCO3, CaCO3, Ca(HCO3)2.
  • Thus, the present invention provides an improved process for carbon capture in accordance with the claims appended hereto.
  • There now follows a detailed description of the invention, which is to be read with reference to the accompanying drawings in which:
    • Figure 1 illustrates a graph of carbon dioxide capture rate and fluid bed pressure drop against L/G;
    • Figure 2 is illustrative of a flue gas cleaning plant; and,
    • Figure 3 is illustrative of a carbon dioxide capture and algae tank for photosynthesis.
    • Figure 1 shows the relationship between both CO2 removal efficiency & pressure loss through the fluid bed versus L/G ratio for a bed of selected hollow, generally acorn shaped but distended elements made in polypropylene known as TurboPakRTM in a test tower of 200mm diameter and with a superficial gas velocity of 0.9m/s.
  • The CO2 was captured in to a semi saturated aqueous solution of Calcium Chloride of about 50% of its pure CaCl2(aq) solubility limit in water at 12°C, (i.e. at about 31.5g of CaCl2(c) per 100g of water or 2.84mol/litre) being the average temperature of the tested saline solution through the scrubber tower, the saline solution having an Ionic Strength of about 8.5mol/litre.
  • Other fluidised bed elements are able to generate higher interfacial areas and, hence, greater capture efficiencies and lower pressure drops.
  • One proposed application of the process is shown in Figure 2, whereby the CO2 is captured from a dirty flue gas in a fluid bed scrubber (TurboScrubberRTM) then cycled rapidly to a fluid bed stripper (TurboStripperRTM) where it is desorbed in to a clean air stream for introduction to a horticultural glass-house to enhance fruit, vegetable or other crop growth.
  • Another proposed application of the novel process provided by the present invention is illustrated in Figure 3, in which process, either CO2 enriched salt water is circulated through a tank 7 containing Algae to feed the Algae, to allow fast photosynthesis to occur in, for example, the production of bio-fuels, or the Algae suspension, if sufficiently robust, can be pumped around the Turboscrubber RTM 2 and the Algae tank 7 to keep it in constant contact with the CO2 enriched aqueous solution.
  • The TurboscrubberRTM is provided with:
    1. a) an inlet 1 for the introduction of flue gas;
    2. b) an outlet 6 for gas of reduced CO2 content; and,
    3. c) a outlet line 5 including a pump 3 for for feeding the treated flue gas to the Algae tank 7.
  • The Algae tank 7 comprises an optional stirrer 9, a bleed valve 8 and on outlet line with a return pump 10 in a line 10a for recirculating treated flue gas to the Turboscrubber RTM2.
  • An optional Algae recycling line 4 is provided between the line 5 and the recirculating line 10a, see Figure 3.
  • Modifications may be made to the above described development within the scope of the claims appended hereto.

Claims (6)

  1. A process for absorption of carbon dioxide gas in a liquid, which process comprises:
    (i) providing a fluidised bed scrubber having a fluidised bed comprising hollow plastics elements; and
    (ii) using the hollow plastics elements in the fluidised bed to cause mixing of counter-current flowing streams of liquid and gas,
    and characterised in that the process comprises:
    (iii) using a combination of liquid to gas ratios of at least 20 litres/m3 and simultaneously using saline solutions with an Ionic Strength of at least 0,2 mol/l,
    whereby the carbon dioxide gas is absorptively captured in the liquid such that the carbon dioxide gas does not react with the liquid to produce carbon dioxide products by chemical reaction.
  2. A process according to claim 1 in which the hollow plastics elements are of a shape and size which cause a contact and interfacial area between the counter-current gas and liquid streams to be such as to minimize gaseous flow pressure drop and to avoid "flooding".
  3. A process according to claim 1 or claim 2 in which the concentration of the carbon dioxide in the gas phase is in excess of 1% by volume.
  4. A process according to any one of the preceding claims in which the absorptively captured carbon dioxide is removed from the liquid phase by cycling the liquid to a stripping device which enables desorption of the carbon dioxide to take place within a few minutes of the absorptive capture of the carbon dioxide.
  5. A process according to claim 4 in which the stripping device is a fluidised bed.
  6. A process according to any one of the preceding claims in which the solvent is water.
EP16716640.4A 2015-04-02 2016-03-22 Process for the absorption of carbon dioxide Active EP3277407B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1505737.5A GB2538484A (en) 2015-04-02 2015-04-02 Improvements in or relating to carbon capture
PCT/GB2016/000057 WO2016156771A1 (en) 2015-04-02 2016-03-22 Improvements in or relating to carbon capture

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EP3277407A1 EP3277407A1 (en) 2018-02-07
EP3277407B1 true EP3277407B1 (en) 2021-06-16

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WO (1) WO2016156771A1 (en)

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US12358813B2 (en) 2019-03-18 2025-07-15 Noram Engineering And Constructors Ltd. Kraft pulping foul condensate treatment process and apparatus
TWI758610B (en) * 2019-06-12 2022-03-21 林正仁 Gas treatment method

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MX2011002120A (en) * 2008-08-28 2011-03-28 Orica Explosives Tech Pty Ltd Improved integrated chemical process.
GB2464763B (en) * 2008-10-29 2010-10-27 Raffael Jovine Method of carbon sequestration
US8394350B2 (en) * 2009-05-28 2013-03-12 Lawrence Livermore National Security, Llc Catalyst functionalized buffer sorbent pebbles for rapid separation of carbon dioxide from gas mixtures
EP2490791B1 (en) * 2009-08-04 2017-07-05 CO2 Solution Inc. Process for co2 capture using carbonates and biocatalysts
EP2461893A4 (en) * 2009-08-04 2013-01-09 Co2 Solution Inc FORMULATION AND METHOD FOR CO2 CAPTURE USING AMINO ACIDS AND
CN102811793B (en) * 2010-05-26 2014-11-26 艺科环球科技私人有限公司 Methods and system for removing gas components from flue gas
JP6219292B2 (en) * 2011-10-28 2017-10-25 ローレンス リバーモアー ナショナル セキュリティー， エルエルシー Carbon-encapsulated liquid encapsulated in polymer to allow solid precipitation for increased capacity
US20140217017A1 (en) * 2013-02-04 2014-08-07 Climate Restoration Technologies, Inc. Transforming energy and transportation into primary engines for reversing global warming and eliminating ocean acidification

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EP3277407A1 (en) 2018-02-07
GB201505737D0 (en) 2015-05-20
GB2538484A (en) 2016-11-23
US20180117525A1 (en) 2018-05-03
WO2016156771A1 (en) 2016-10-06

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